Vat dye and process of making same.



UNITED snares. eerie.

\RMIN GROB, OF BASEL, SWITZERLAND, ASSIGNOR TO BASLE (HEMIiAL-WORKS, OF BASEL SWITZERLAND.

.VAT DYE Al TD PROCESS OF MAKING SAME.

Specification of Letters fatent.

Patented March 1c, 1905;.

Application filed October s, 1908. Serial in. 456,436.

To all whom it may concern: Be It known that I, ARMIN GROB, a citizen of the Swiss Republic, and resident of Basel,

Switzerland, have invented a new Vat Dyestuif and a Process of Making Same, of which the following is a full, clear, and exact specification.

l have found that by reacting with ace naphthene-quinone upon a derivative of 3-oxy-1-thio-naphthene having a substituent in the benzene nucleus a new vat-dyestuff is obtained. In this reaction the derivative of 3-oxy-1-thio-naphthene can be produced in the reaction mass itself by heating the corres onding derivative of phenylthioglycollicort ocarboxylic acid with the acenaphthenequinone employed. The said reaction can further be carried out in the presence or not of a dissolvent or of a condensing agent. The vat-dyestuffs thus obtained constitute in dry state, yellow-red to brownish powders which dissolve in concentrated sulfuric acid to green to blue solutions from which they are precipitated again on addition of water and are somewhat difficultly soluble in hot benzene to reddish orange to orange solutions. They dye unmordanted cotton from reducedgilkaline vat tints being after oxidation red to orange.

The manufacture of the new dyestuffs is ex lained by the following examples:

xample I: 25 parts of 2-phenylthiogly collic-4-chloro-1-carboxylic acid, of the formula coon (1 o n son ooou 2 and 18.5 parts of finely powdered aoenaphthene-quinone are heated together quickly in a bath at 220250 C. until the elimination of water and formation of dyestuli are at an end; the red-brown mass is exhausted of the dyestuff by extraction with much boiling benzene. The condensation can also be effected by heating to the same temperature in presence of an indilferent solvent, for instance parts of naphthalene; or the mixture may be heated for some time in presence of 100 parts of acetic anhydrid and 3 parts of sodium acetate in a bath at 135150 (3., a reflux condenser being used.

The, dyestuff is a yellow red to brownish crystalline powder. It dissolves in concentrated sulfuric acid to a green solution from which it is precipitated again on addition of water. in hot benzene it is somewhat difficultly soluble to a reddish-orange solution. When finely divided it easily yields a violet vat. by treatment with alkaline sodium hydrosulfite solution, from which vat cottonwithout a niordant and subsequently subjected to oxidation is dyed yellow red tints.

in this example the phenyl-thio-glycollicd-chloro-l-carb'oxylic acid employed is during the heating of the reaction mass transformed intermediary into the corresponding chlorc derivative of 3-oxy-1-thiona phthene and can therefore be replaced by this latter.

inthis example for the 2-phenylthioglycollic-i-chloro-l-carboxylic acid, or the oxythionaphthene derivative obtainable therefrom, may also be substituted the corresponding bromo-compounds in which the bromin is in the d position.

Example 11:20 parts of e-ethylthiooxythionaphthene of the formula 1 c ange s/ and libparts of finely pulverized acenaph thene-o uinonej are suspended or dissolved in 1000 parts of boiling spirit, then mixed with an aqueous solution of 3 parts of calcined soda or g a corresponding quantity of ammonia or sodium hydroxid in 100 parts of water, and kept boiling in a reflux apparatus until separation of the dyestufi is complete. The dyestufi', an orange red precipitate, is filtered, washed and dried. It dissolves somewhat difficultly in hot benzene to an orange solution. In concentrated sulfuric acid. it dissolves'to a greenish-blue solution and is again precipitated on addition of water. With alkaline sodium hydrosulfite solution a vat is obtained with which cotton without a mordant can be dyed orange tints.

in this example for the 4-ethylthiooXy thionaphthene may be substituted 4-ethoxyoxythionaphthene.

V'Vhat I claim is:

1. The described rocess for the manufacture of vat-dyestu s consisting in heating acenaphthene-quinone with a derivative of 3-oxy1thionaphthene having a substituent in the benzene nucleus.

2. The described rocess for the manufacture of vat-dyestu s consisting in heating acenaphthene-quinone with a derivative of phenylthioglycollic-orthocarboxylic acid, this latter being intermediary transformed into ture of a red vat-dyestuff consisting in heati ing acenaphthenequinone with a halogen, derivative of phenylthioglycollic-orthocarboxylie acid, this'latter being intermediary transformed into the corresponding halogen derivative of 3 oxy-l-thionaphthene.

5. The described process for the manul'acture of a red vat-dyestufi' consisting in heating acenaphthenequinone with a chloro derivative of 3-oxy-l-thionaphthene.

6. The described process for the manufacture of a red vat-dyestufl' consisting in heating acenaphthene-quinono with 2-phenylic-4-chloro-1carboxylic acid, this latter being intermediary transformed into the corresponding chloro derivative of 3- oxy-l-thionaphthene:

7. As new products, the herein described l vat-dyestuffs derived from acenaphthenequinone and a derivative of 3-oxy-1-thionaphthene, constituting in dry state, yellowred to brown powders, dissolving in concena trated sulfuric acid to green to blue solutions y from which they are precipitated again on low-red to orange.

{ addition of water, somewhat diflicultly'solui herein described red vat-dyestufi derived i from acenaphthene-quinone and a chloro derivative of 3-oxy-1-thionaphthene, cone stituting, in drystate, a yellow-red to brownish crystalline powder, dissolving in concentratedsulfuric acid to a green solution from which it is precipitated again on addition of water, somewhat difficultly soluble in hot benzene to a reddish orange solution and yielding by alkaline reduction a violet vat from which cotton is dyed tints being after oxidation yellow-red.

In Witness whereof I have hereunto signed my name this th day of September 1908, in the presence of two subscribing witnesses.

, ARMIN eRoB.

Witnesses ERNST WAGNER, AMAND RITTER.

8. As a new article of manufacture, the 

